Method of making doped Alq3 nanostructures with enhanced photoluminescence

ABSTRACT

A method of making doped Alq 3  nanostructures with enhanced photoluminescence is provided. The method of making doped Alq 3  nanostructures with enhanced photoluminescence includes the steps of dissolving tris(8-hydroxyquinolinato)aluminum (Alq 3 ) and a metal in water to form a solution. The metal may be terbium (Tb), copper (Cu), silver (Ag), dysprosium (Dy) or europium (Eu), for example. The metal may be provided in a water soluble form, such as chlorides and nitrates thereof. The solution is then subjected to ultrasonic waves (i.e., a sonication bath) for a period of approximately 3 hours to approximately 4 hours. The solution is then dried at a temperature of approximately 50° C. for a period of approximately 8 hours to form a powder of Alq 3  doped with the metal. The powder is then formed into nanostructures of the Alq 3  doped with the metal.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to photoluminescent materials, such as those used in organic light emitting diodes (OLEDs), and particularly to a method of making doped tris(8-hydroxyquinolinato)aluminum (Alq₃) nanostructures having enhanced photoluminescence.

2. Description of the Related Art

Tris(8-hydroxyquinolinato)aluminum (Al(C₉H₆NO)₃) is a coordination complex where aluminum is bonded in a bidentate manner to the conjugate base of three 8-hydroxyquinoline ligands. Tris(8-hydroxyquinolinato)aluminum (commonly referred to as Alq₃) is a common component of organic light emitting diodes (OLEDs). Variations in the substituents on the quinoline rings affect its luminescence properties. Primarily, Alq₃ is used as the material for the electron-transport layer and also as the host for the emitter layer in OLEDs.

The ligand, quinolinolate, has long been used as a complexing agent in a wide variety of analytical techniques. Alq₃ is an octahedrally coordinated chelate complex of the type M(NO)₃, where M is a trivalent metal and N and O are the nitrogen and oxygen atoms in the bidentate quinolinolate ligand. Because of the bidentate nature of the ligand, the Alq₃ complex can occur in two isomeric forms, namely, a facial isomer and a meridional isomer, depending on the orientations of the ligands.

Recently, there has been research on fabricating Alq₃ in nanostructure form. For example, Alq₃ spherical nanoparticles have been fabricated by vapor condensation, having an average size varying between 50 nm and 500 mm. The photoluminescence (PL) spectra of the nanoparticles showed a broadened peak varying from 450 nm to 700 nm. It was reported that the maximum intensity increased as the particle size decreased, due to the large specific surface area. Other techniques for the manufacture of nano-crystals of Alq₃ have been reported, such as through the use of solvents. Additional research has gone into the improvement of the luminescence properties of Alq₃ through the addition of other materials, however only very limited improvements have been reported.

At the nanoscale, many properties of Alq₃ can be improved, particularly through doping with proper activators. In order to enhance the photoluminescence of Alq₃, for use in OLEDs and the like, it would be desirable to efficiently and effectively synthesize doped Alq₃, at the nanoscale level, by incorporating different impurities in the host.

Thus, a method of making doped Alq₃ nanostructures with enhanced photoluminescence solving the aforementioned problems is desired.

SUMMARY OF THE INVENTION

The method of making doped Alq₃ nanostructures with enhanced photoluminescence includes the steps of dissolving tris(8-hydroxyquinolinato)aluminum (Alq₃) and a metal in water to form a solution. The metal may be terbium (Tb), copper (Cu), silver (Ag), dysprosium (Dy) or europium (Eu), for example. The metal may be provided in a water soluble form, such as chlorides and nitrates thereof. The solution is then subjected to ultrasonic waves (i.e., a sonication bath) for a period of approximately 3 hours to approximately 4 hours. The solution is then dried at a temperature of approximately 50° C. for a period of approximately 8 hours to form a powder of Alq₃ doped with the metal. The doped Alq₃ powder can be used to form nanostructures. For example, the doped Alq₃ powder can be used to form nanorods and nanostructure films by a physical vapor condensation method. The doped Alq₃ powder can be used to form nanofibers by an electrospinning technique. Nanoparticles and nanowire films may be formed by physical vapor condensation of the powder, and nanofibers may be formed by electrospinning of the powder. A dysprosium (Dy) dopant in Alq₃ nanorods, nanowires and nanofibers is found to increase photoluminescence (PL) intensity by a factor of four when compared against undoped Alq₃.

These and other features of the present invention will become readily apparent upon further review of the following specification and drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph illustrating X-ray diffraction results for doped Alq₃ film prepared by physical vapor condensation (curve “a”), as well as X-ray diffraction results for doped Alq₃ powder (curve “b”), each prepared by the method of making doped Alq₃ nanostructures with enhanced photoluminescence according to the present invention.

FIG. 2 is a graph comparing the photoluminescence (PL) emission spectra of Alq₃ powder (curve “a”); pure Alq₃ nanoparticles (curve “b”); Alq₃ nanoparticles doped with Tb (curve “c”), prepared by the method of making doped Alq₃ nanostructures with enhanced photoluminescence; Alq₃ nanoparticles doped with Cu (curve “d”), prepared by the method of making doped Alq₃ nanostructures with enhanced photoluminescence; and Alq₃ nanoparticles doped with Ag (curve “e”), prepared by the method of making doped Alq₃ nanostructures with enhanced photoluminescence.

FIG. 3 is a graph comparing the photoluminescence (PL) emission spectra of Alq₃ powder (curve “a”); pure Alq₃ nanorods (curve “b”); Alq₃ nanorods doped with Tb (curve “c”), prepared by the method of making doped Alq₃ nanostructures with enhanced photoluminescence; Alq₃ nanorods doped with Cu (curve “d”), prepared by the method of making doped Alq₃ nanostructures with enhanced photoluminescence; Alq₃ nanorods doped with Ag (curve “e”), prepared by the method of making doped Alq₃ nanostructures with enhanced photoluminescence; Alq₃ nanorods doped with Dy (curve “f”), prepared by the method of making doped Alq₃ nanostructures with enhanced photoluminescence; and Alq₃ nanorods doped with Eu (curve “g”), prepared by the method of making doped Alq₃ nanostructures with enhanced photoluminescence.

FIG. 4 is a graph comparing the photoluminescence (PL) emission spectra of Alq₃ powder (curve “a”); pure Alq₃ nanorods/nanowires (curve “b”); Alq₃ nanorods doped with Dy at an Alq₃ to Dy ratio of 1 to 0.1 by weight (curve “c”), prepared by the method of making doped Alq₃ nanostructures with enhanced photoluminescence; Alq₃ nanorods doped with Dy at an Alq₃ to Dy ratio of 1 to 0.15 by weight (curve “d”), prepared by the method of making doped Alq₃ nanostructures with enhanced photoluminescence; Alq₃ nanorods doped with Dy at an Alq₃ to Dy ratio of 1 to 0.2 by weight (curve “e”), prepared by the method of making doped Alq₃ nanostructures with enhanced photoluminescence; and Alq₃ nanorods doped with Dy at an Alq₃ to Dy ratio of 1 to 0.25 by weight (curve “f”), prepared by the method of making doped Alq₃ nanostructures with enhanced photoluminescence.

FIG. 5 is a graph comparing the photoluminescence (PL) emission spectra of Alq₃ powder (curve “a”); pure Alq₃ nanofibers (curve “b”); Alq₃:PVA nanofibers doped with Tb (curve “c”), prepared by the method of making doped Alq₃ nanostructures with enhanced photoluminescence; Alq₃:PVA nanofibers doped with Cu (curve “d”), prepared by the method of making doped Alq₃ nanostructures with enhanced photoluminescence; Alq₃:PVA nanofibers doped with Ag (curve “e”), prepared by the method of making doped Alq₃ nanostructures with enhanced photoluminescence; Alq₃:PVA nanofibers doped with Dy (curve “f”), prepared by the method of making doped Alq₃ nanostructures with enhanced photoluminescence; and Alq₃:PVA nanofibers doped with Eu (curve “g”), prepared by the method of making doped Alq₃ nanostructures with enhanced photoluminescence.

FIG. 6 is a graph comparing the photoluminescence (PL) emission spectra of Alq₃ powder (curve “a”); Alq₃:PVA nanofibers doped with Dy at an Alq₃ to Dy ratio of 1 to 0.05 by weight (curve “b”), prepared by the method of making doped Alq₃ nanostructures with enhanced photoluminescence; Alq₃:PVA nanofibers doped with Dy at an Alq₃ to Dy ratio of 1 to 0.1 by weight (curve “c”), prepared by the method of making doped Alq₃ nanostructures with enhanced photoluminescence; Alq₃:PVA nanofibers doped with Dy at an Alq₃ to Dy ratio of 1 to 0.15 by weight (curve “d”), prepared by the method of making doped Alq₃ nanostructures with enhanced photoluminescence; Alq₃:PVA nanofibers doped with Dy at an Alq₃ to Dy ratio of 1 to 0.2 by weight (curve “e”), prepared by the method of making doped Alq₃ nanostructures with enhanced photoluminescence; and Alq₃:PVA nanofibers doped with Dy at an Alq₃ to Dy ratio of 1 to 0.25 by weight, prepared by the method of making doped Alq₃ nanostructures with enhanced photoluminescence.

Similar reference characters denote corresponding features consistently throughout the attached drawings.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The method of making doped Alq₃ nanostructures with enhanced photoluminescence includes the steps of dissolving tris(8-hydroxyquinolinato)aluminum (Alq₃) and a metal in water to form a solution. The metal may be terbium (Tb), copper (Cu), silver (Ag), dysprosium (Dy) or europium (Eu), for example. The metal may be provided in a water soluble form, such as chlorides and nitrates thereof. The solution is then subjected to ultrasonic waves (i.e., a sonication bath) for a period of approximately 3 hours to approximately 4 hours. The solution, including the dissolved Alq₃ powder preferably has an Alq₃ to metal ratio of approximately 1 to 0.2 by weight or approximately 1 to 0.1 by weight. The solution is then dried at a temperature of approximately 50° C. for a period of approximately 8 hours to form a powder of Alq₃ doped with the metal. The powder is then formed into nanostructures of the Alq₃ doped with the metal. The doped Alq₃ powder can be used to form nanoparticles, nanorods, and nanowire films by physical vapor condensation as described herein. Nanofibers may be formed by an electro spinning technique described herein. The nanostructures may then be used in organic light emitting diodes (OLEDs) or the like, in a manner similar to conventional, undoped Alq₃. As will be discussed in greater detail below, a dysprosium (Dy) dopant in Alq₃ nanorods, nanowires and nanofibers is found to increase photoluminescence (PL) intensity by a factor of four when compared against undoped Alq₃.

In an exemplary method, Alq₃ doped with silver was prepared by dissolving about 100 mg of AgNO₃ powder in about 20 mL of double distilled water. About 0.5 g of Alq₃ was then added to the solution. The solution was sonicated and then dried to obtain a powder. Physical vapor condensation was then performed to form nanostructures of the Alq₃ doped with the metal. In detail, approximately 0.1 grams of the doped Alq₃ powder were held in a molybdenum boat. Glass substrates were used to deposit the nanomaterials. The substrate was placed above the boat at a distance of approximately 10 cm. The chamber of the system was evacuated to a pressure on the order of 10⁻⁶ torr, then the source material was heated to a temperature of 450° C., at a heating rate of 5° C./min. To grow Alq₃ nanorod/nanowire films, physical vapor condensation was used with a cold trap. In detail, the doped powder sample was evaporated on a graphite boat, with a glass slide used as the substrate to deposit the nanomaterials. The substrate was fixed in a liquid nitrogen cooled holder.

The doped Alq₃ powder can be used to prepare nanofibers by electrospinning. In an exemplary method, the doped Alq₃ powder was dissolved in water (about 10 mL) and mixed with highly pure polyvinyl alcohol (PVA) (Alq₃:PVA weight ratio of 0.2:1). The solution was stirred for about 4 hours with heating at about 80° C. to form a viscous solution. Then, approximately 10 mL of this solution was held in a syringe and fixed in the electrospinning system. The applied voltage was 23 kV and the feeding rate was 0.2 mL/hour. The tip collector distance was 100 mm. The nanofibers were collected on a glass slide for about 4 hours. The ratios of Alq₃ to dopant by weight were 1:0.1.

As shown in FIG. 1, nanostructures of Alq₃ were characterized by X-ray diffraction (Cu Kα radiation, λ=1.5418 Å wavelength, at a 40 kV accelerating voltage and a 30 mA current) with an UltimaIV diffractometer (Rigaku, Japan), using parallel beam geometry and a multi-purpose thin film attachment. For all films containing nanostructures of Alq₃, the XRD patterns were recorded in θ-2θ, with a grazing incidence angle of 1°, for an angular interval of 10°-80°, with a 0.05° step-size and a 2 second count time per step. In FIG. 1, curve “a” illustrates the X-ray diffraction results for doped Alq₃ film prepared by physical vapor condensation, as described above, and curve “b” illustrates the X-ray diffraction results for the doped Alq₃ powder itself. The morphology of the films was analyzed with field emission scanning electron microscopy (FESEM), operated at 10-20 kV, and also with tapping-mode atomic force microscopy (AFM) with a scanning area of 500 nm×500 nm. The system is a variable temperature UHV AFM/STM model XA 50/500, Omicron, Germany.

Photoluminescence emission spectra of pure and doped Alq₃ nanostructures were recorded at room temperature using a fluorescence spectrofluorophotometer (model RF-5301 PC, Shimadzu, Japan). FIG. 2 shows the photoluminescence (PL) emission spectra of the “original” Alq₃ powder (i.e., prior to any mixing or dissolving thereof) (curve “a”); pure Alq₃ nanoparticles (prepared via the above method, but without doping) (curve “b”); Alq₃ nanoparticles doped with Tb (curve “c”); Alq₃ nanoparticles doped with Cu (curve “d”); and Alq₃ nanoparticles doped with Ag (curve “e”).

FIG. 3 shows the photoluminescence (PL) emission spectra of the “original” Alq₃ powder (curve “a”); pure Alq₃ nanorods (curve “b”); Alq₃ nanorods doped with Tb (curve “c”); Alq₃ nanorods doped with Cu (curve “d”); Alq₃ nanorods doped with Ag (curve “e”); Alq₃ nanorods doped with Dy (curve “f”); and Alq₃ nanorods doped with Eu (curve “g”). For curves c through g, the Alq₃ to dopant ratio is 1 to 0.1 by weight. As noted above, doping with Dy has shown to generate the greatest enhancement in photoluminescence.

FIG. 4 shows the photoluminescence (PL) emission spectra of the “original” Alq₃ powder (curve “a”); pure Alq₃ nanorods/nanowires (curve “b”); Alq₃ nanorods doped with Dy at an Alq₃ to Dy ratio of 1 to 0.1 by weight (curve “c”); Alq₃ nanorods doped with Dy at an Alq₃ to Dy ratio of 1 to 0.15 by weight (curve “d”); Alq₃ nanorods doped with Dy at an Alq₃ to Dy ratio of 1 to 0.2 by weight (curve “e”); and Alq₃ nanorods doped with Dy at an Alq₃ to Dy ratio of 1 to 0.25 by weight (curve “f”). As shown, a ratio of 1 to 0.2 by weight produces the greatest photoluminescence enhancement.

FIG. 5 shows the photoluminescence (PL) emission spectra of the “original” Alq₃ powder (curve “a”); pure Alq₃ nanofibers (curve “b”); Alq₃:PVA nanofibers, prepared as described above, doped with Tb (curve “c”); Alq₃:PVA nanofibers doped with Cu (curve “d”); Alq₃:PVA nanofibers doped with Ag (curve “e”); Alq₃:PVA nanofibers doped with Dy (curve “f”); and Alq₃:PVA nanofibers doped with Eu (curve “g”). For curves c through g, the Alq₃ to dopant ratio is 1 to 0.1 by weight. Similar to Alq₃, the Alq₃:PVA nanofibers exhibit the greatest enhancement in photoluminescence by doping with Dy. Confocal image and photoluminescence emission spectra of the nanofiber samples were carried out using Laser-scanning Fluorescence Confocal Microscopy (LSM 780 Carl Ziess, Germany). The used excitation source is a violet laser diode of 405 nm CW.

FIG. 6 shows the photoluminescence (PL) emission spectra of the “original” Alq₃ powder (curve “a”); Alq₃:PVA nanofibers doped with Dy at an Alq₃ to Dy ratio of 1 to 0.05 by weight (curve “b”); Alq₃:PVA nanofibers doped with Dy at an Alq₃ to Dy ratio of 1 to 0.1 by weight (curve “c”); Alq₃:PVA nanofibers doped with Dy at an Alq₃ to Dy ratio of 1 to 0.15 by weight (curve “d”); Alq₃:PVA nanofibers doped with Dy at an Alq₃ to Dy ratio of 1 to 0.2 by weight (curve “e”); and Alq₃:PVA nanofibers doped with Dy at an Alq₃ to Dy ratio of 1 to 0.25 by weight. As shown, similar to Alq₃ nanorods/nanofibers, a ratio of 1 to 0.2 by weight produces the greatest photoluminescence enhancement.

It is to be understood that the present invention is not limited to the embodiments described above, but encompasses any and all embodiments within the scope of the following claims. 

We claim:
 1. A method of making doped Alq₃ nanostructures with enhanced photoluminescence, comprising the steps of: dissolving tris(8-hydroxyquinolinato)aluminum (Alq₃) and a metal in water to form a solution, wherein the metal is selected from the group consisting of dysprosium and europium: sonicating the solution; drying the solution to form a powder of Alq₃ doped with the metal; and forming the powder into nanofibers of the Alq₃ doped with the metal by electrospinning.
 2. The method of making doped Alq₃ nanostructures with enhanced photoluminescence as recited in claim 1, wherein the metal comprises dysprosium.
 3. The method of making doped Alq₃ nanostructures with enhanced photoluminescence as recited in claim 1, wherein the step of sonicating the solution comprises sonicating the solution for approximately 3 to approximately 4 hours.
 4. The method of making doped Alq₃ nanostructures with enhanced photoluminescence as recited in claim 3, wherein the solution has an Alq₃ to metal ratio of approximately 1 to 0.2 by weight.
 5. The method of making doped Alq₃ nanostructures with enhanced photoluminescence as recited in claim 4, wherein the step of drying the solution to form the powder of Alq₃ doped with the metal comprises drying the solution at a temperature of approximately 50° C. for approximately 8 hours.
 6. A method of making doped Alq₃ nanostructures with enhanced photoluminescence, comprising the steps of: dissolving tris(8-hydroxyquinolinato)aluminum (Alq₃) and a metal in water to form a solution, wherein the metal is selected from the group consisting of dysprosium and europium; sonicating the solution; drying the solution to form a powder of Alq₃ doped with the metal; and forming the powder into nanostructures of the Alq₃ doped with the metal.
 7. The method of making doped Alq₃ nanostructures with enhanced photoluminescence as recited in claim 6, wherein the metal comprises dysprosium.
 8. The method of making doped Alq₃ nanostructures with enhanced photoluminescence as recited in claim 6, wherein the step of sonicating the solution comprises sonicating the solution for approximately 3 to approximately 4 hours.
 9. The method of making doped Alq₃ nanostructures with enhanced photoluminescence as recited in claim 8, wherein the solution has an Alq₃ to metal ratio of approximately 1 to 0.2 by weight.
 10. The method of making doped Alq₃ nanostructures with enhanced photoluminescence as recited in claim 9, wherein the step of drying the solution to form the powder of Alq₃ doped with the metal comprises drying the solution at a temperature of approximately 50° C. for approximately 8 hours.
 11. The method of making doped Alq₃ nanostructures with enhanced photoluminescence as recited in claim 6, wherein the step of forming the powder into nanostructures of the Alq₃ doped with the metal comprises physical vapor condensation.
 12. The method of making doped Alq₃ nanostructures with enhanced photoluminescence as recited in claim 6, wherein the step of forming the powder into nanostructures of the Alq₃ doped with the metal comprises electrospinning.
 13. A method of making doped Alq₃ nanostructures with enhanced photoluminescence, comprising the steps of: dissolving tris(8-hydroxyquinolinato)aluminum (Alq₃) and a metal in water to form a first solution; sonicating the first solution; drying the first solution to form a first powder of Alq₃ doped with the metal; dissolving the first powder and polyvinyl alcohol in water to form a second solution; stirring the second solution; and forming the second solution into nanofibers of the Alq₃ doped with the metal by electrospinning.
 14. The method of making doped Alq₃ nanostructures with enhanced photoluminescence as recited in claim 13, wherein the step of dissolving the first powder and the polyvinyl alcohol in the water to form the second solution comprises dissolving the first powder and the polyvinyl alcohol in the water, wherein a ratio of the first powder to the polyvinyl alcohol in the second solution is approximately 0.2 to 1 by weight.
 15. The method of making doped Alq₃ nanostructures with enhanced photoluminescence as recited in claim 13, wherein the step of stirring the second solution comprises stirring the second solution for approximately 4 hours.
 16. The method of making doped Alq₃ nanostructures with enhanced photoluminescence as recited in claim 15, wherein the step of stirring the second solution is performed at a temperature of approximately 80° C. 